Preparation of aldehydes by steam oxidation of ethers



( P .i'ui zama I amm j mummior amnnrnns at small OXIDATION or mass rm r. "as, Baton Rouge, 1..., assignorto Standard Oil Development Company, a corporation of Delaware No Application January 25.1946, y a Serial No. 043.411 i Q 4 Claims. (01. zoo-s01) g2 This invention relates to. a methodoi utilizing 7 effect at moderately elevatedtemperatures in the I .an aliphatic ether to produce an aldehyde. More particularly, it relates to the conversion of a volatile saturated aliphatic ether, such as ethyl f ether, to a corresponding aldehyde.

Since large quantities of aliphatic ethers have been made available as by-products in synthwizing alcohols from oleilns, there has been a need for practical methods of converting the ethers toother commercially useful products.

It is known from classical organic chemistry:

range of about 750 F. to 950 F. By having the catalyst exert a markeddehydrogenating eflect at thesetemperatures. the dehydrating and splitting conversion of ethers to alcohols and oleflns is suppressed. Therefore, highly active dehydrothat ethers are slowly hydrolyzed or hydrated on heating with diluteacids 1 1 1,;

Methods have been proposed'for obtaininghydration of ethers to alcohols more rapidly by using steam under high pressures and a solid hydrating catalyst. It has been reported that a 23% yield of ethyl alcohol is obtained by reacting diethyl ether with steam attemperatures' below 000 F. in the presence of alumina and that at with steam under selective dehydrogenation conditions which favor aldehyde formation.

Ethers are known to be-stable compounds in corresponding which the oxygenbridge 0-0-0 is diilicult to disrupt. Cleavage of this bridge is obtained under certain' conditions of double decomposition with steam or acids and generally the cleavage hasled to the formation of alcohols.

While investigating the possibility of selectively.

. removinglhydrogen from C C links in an ether without cleavage. as, for example. in catalytically 1 dehydrogenating diethyl to vinyl ether, I dis-;

covered conditions under which the reaction went beyond unsaturation of 0-0 links to a cleavage of the oxygen bridge that resulted in aldehyde formation. The net reaction in the conversion of the ether to aldehyde may be represented by the fol-- lowing equation:

cmon+mo+2cn5ciro+flm an important factor in this selective conversion o! ethers to aldehydes is now found tells the use of a catalysthaving a markeddehydrogenating covered. In another runat 800 F., a 20% yield nickel, platinum, palladium. and similar substances known to be highly active in both hydrogenating and dehydrogenating reactions. To someextentmetal oxide catalysts of hydrogenating-dehydrogenatlng activity at temperatures in the range of 750 to 950-F. may be used, as for example oxides of'chromium and molybdenum. Also, the active hydrogenating-dehydrogenating catalysts arefpreferably used supported on carriers such as clay, alumina, silica gel. or metal oxides which promote activity of the catalyst.

aldehydes is control of the proportion of steam. 'I'hepre'ferred proportion of steam is approximately the stoichiometric equimolar amount with respect to the ether. The ratio of steam to ether may vary from about V to 1 mole of steamper 'mole of ether.

Adjustment of contact time of feed rate may be made for specific catalyst activity, specific reaetants; concentrations of the reactants, tempera ture, pressure, and yield rate desired. A practical feed rate is a space velocity of about 1.8 volumes of liquid reactants per volume of catalyst per hour, or in the range of about 0.5 to 2 liquid volumes per volume of catalyst per hour.

Preferred modes of conducting conversion are indicatedby the following illustrative examples, which are not intended to limit the invention:

Examples Runs were made with feeds containing approximately equimolar proportions of diethyl ether and steam at a-feed rate of 1.8 liquid volume per volume catalyst per hour. The feed was passed over a supported copper catalyst. In one run carried out at 750 F., 5% acetaldehyde was reof acetaldehyde resulted.

As the reaction temperature was raised above 750 F. to temperatures in the range of 800 F. to

. 850 l"., the aldehyde yield was increased to an optimum andan approximate upper limit of the reaction temperature was indicated to be about 950 F., above which excessive decomposition tendstooccur.

Most satisfactory yields are obtained with it Another factor in the selective conversion to I metal catalyst, e. a. copper.

on an adsorbentclay support suchasAt clay. is a satisfactory s pport for the metal catalysts, Moos. or chormch desired reaction. I

The reactants are preferably maintained-under low pressure which Varieswith the reaction temfperature and the vapor pressures oi. the reactants. In converting .diethyl ether at 800 It. the pressure in the reaction. zone is preferably about.

pounds per q inchyabsolutegbutdower or somewhat higher pressures may be used.

The selective conversion oi ethers to' aldehydes may be applied to various mixed or simple aliphatic ethers. but is most advantageous when applied todiethyl ether. It may also be appiied to unsaturated aliphatic ethers, such as vinyl ether, or in general to C4 to C0 aliphatic ethers.

Various forms oi apparatus may be'used i'orv carrying out the process. The catalyst may be used in a fixed or be suspended in the reaction mixture. Unreacted ether may be recycled to enhance the ultimate yield of aldehyde. Also.- an

aqueous distillate phase from which aidehyde product. is separated may be vaporized and used in a reactor to supply steam and reactants convertible to aldehyde product under the conditions describ'ed'to obtain additional yields of aldehyde.

Iclaim:

i 1. The 'method of converting an aliphatic ether I to an aldehyde which comprises contactinga mixture essentially of an aliphatic ether and steam with an active dehydrogenating catalyst at a temperature oi, about 750 F. to 950 F whereby reaction is promoted between the ether and steam the ratio oi the v steam to the ether being from $5 to 1 mole of steam per mole oi ether. 2. The method of converting an aliphatic ether to an aldehyde which comprises contacting ap-* proximately equimolar roportions or ste m and 40 $8,291

am,a1a amusements-museum,-

inalaseswithanactivemotallic ydmenltint cote-intintheranseotflfl'lttoflil'lwhereby reaction is promoud between theet e a s e m.

ae'rhe'method ot eonvertina diethyl ether-to acetaldehyde which comprisa contacting steam 'anddiethyl ether in the absence oi other olidin ins gases with an active dehydrosenatinl catalyst containing copper on a solid adsorbent support at atemperature in the range at 75-9 1''. to 960' volumes, or liquid reactants per volume of catalyst I 7 ram. '1'. mam. I

per hour.

; REFERENCES l'll'lfltl).

The following references are oi record in the me of this patent; H

UNITED s'rs'rss PATENTS Number me 1,859.84 Lloyd et al Mar. 15, 1932 2,031,200 Baur ..4.... Feb. 18,1936

2,148,569 Brown June 24, 1041 FOREIGN Ps'rzm's Number Country 1; Date Germany Oct. 28.1904 

